Metalloid azides and process for preparing the same



3,232,958 METALLOID AZIDES AND PROCESS FOR PREPARING THE SAME Robert M. Washburn, Whittier, Califi, assignor to American Potash 8: Chemical Corporation, Los Angeles, Calif., acorporation of Delaware No Drawing. Filed Nov. 3, 1961, Ser. No. 149,885 10 Claims. (Cl. 260-349) The present invention relates to novel metalloid azides and to processes for preparing the same.

Broadly, the metalloid azides of this invention may be represented by the following formula:

wherein R is selected from the group consisting of aryl, alkyl, halogen, alkoxy, aryloxy, amino, alkylthio, and arylthio groups; M is a metal selected from the group consisting of silicon, germanium, and tin; and n is a Whole number from 1 to 3.

These novel compounds can be prepared by reacting one mole of (a) a compound having the formula wherein R is selected from the group consisting of aryl, alkyl, alkoxy, aryloxy, amino, alkylthio, and arylthio groups; M is a metal selected from the group consisting of silicon, germanium, and tin; X is a halogen atom; and n is a whole number from 1 to 3; with (b) from one to three moles of a compound having the formula MN wherein M is a metal selected from the group consisting of alkali metals and alkaline earth metals.

rates Patent 3,232,958 Patented Feb. 1, 1966 silicon halides which are suitable for use in this invention In carrying out the novel reaction of the present invention, it has been found that for each one mole of compound (a) there must be used from one to three moles of compound (b). The reaction must be carried out under anhydrous conditions to prevent the hydrolysis of the starting metalloid halides and the resulting metalloid azide products. This can be achieved conveniently by carrying out the reaction in an inert atmosphere or under vacuum.

In the formulae above it is indicated that R is selected from a number of listed chemical groups. Examples of slllitable radicals falling within these chemical groups inc ude:

Halogen: F, Cl, Br, I;

include phenyltrichlorosilane, diphenyldibromosilane, triphenylfluorosilane, phenyldimethylbromosilane, diphenylethylfluorosilane, tri-n-propylchlorosilane, phenylidiphenoxychlorosilane, diphenyldimethylaminochlorosilane, trip-tolylchlorosilane, a-naphthylphenylmethylbromosilane, di(o-chlorophenyl)phenylthiobromosilane, tri(m-phenoxyphenyl) chlorosilane, and the like.

Examples of germanium halides which are suitable for use in this invention include phenyldimethylchlorogermane, diphenyldichlorogermane, phenyltribromogermane, tri-n-butylfluorogermane, di(p-tolyl)dibromogermane, anaphthyltrichlorogerman e, phenyldiphenoxychlorogermane, di(o-chlorophenyl)methylthiobromogermane, mtolylmethyldimethylaminobromogermane, and the like.

Examples of tin halides which may be used in this invention include triphenylchlorostanne, diphenyldibromostanne, trimethylfluorostanne, m-tolyltrichlorostanne, tri- (o-chlorophenyl)fluorostanne, di(a-naph.thyl)dibromostarine, tris(dimethylamino)chlorostanne, phenyldiphenylthiochlorostanne, and the like.

In order to illustrate this invention even more fully the following specific examples are set forth.

Example I One mole of triphenylchlorosilane and one mole of sodium azide are refluxed in pyridine for 24 hrs. to yield triphenylazidosilane after removing the sodium chloride by filtration and distilling the solvent.

Example ll When two moles of lithium azide are reacted with one mole of dimethyldichlorosilane in toluene at room temperature for 3 days, a toluene solution of dimethyldiazidosilane is obtained.

' Example III The interaction of phenyltrichlorogermane (one mole) and potassium azide (3 moles) in refluxing acetonitrile for 24 hrs. yields phenyltriazid-ogermane.

Example I V Triethylchlorostanne (1 mole) reacts in toluene with sodium azide (1 mole) to yield triethylazidostanne.

Example V The interaction of phenyldimethylbromosilane (one mole) and sodium azide (one mole) in refluxing pyridine for 36 hrs. yields phenyldimethylaZidost-anne.

In addition to the above described metalloid azides, a class of di'function metalloid azides having the generalized formula shown below also can be synthesized.

In the formula, R and M are as defined above, L is an arylene or alkylene group, and n is a whole number of from 1 to 3.

Examples of suitable arylene and alkylene groupings represented by L in the formula are 1,4-C H 1,3- C H 4,4-C H -OC H 1,4-naphthy1ene; pentarnethylene; and the like.

These difunctional metalloid azides can be prepared by reacting one mole of (i) a difunctional metalloid halide, having the generalized formula shown below,

The following examples illustrate the preparation of difunctional metalloid azides.

Example VI A mixture of one mole of 1,4-Cl SiC H SiCl and 6 moles of lithium azide is refluxed in pyridine for 36 hrs. to 1,4-(N3)3SiC H4-Sl(N3)3' Example VII After one week at room temperature, a mixture of two moles of sodium azide and one mole of 1,3-BrGe (CH C H Ge (CH Br results in the formation of 1,3-N Ge (CH C H -Ge (CH N Example VIII When one mole of 4,4-F Sn(C H )C H -o-C H 4n(C l-I )F and four moles of sodium azide are reacted in xylene solvent at 100 for 48 hrs.

a)2 6 5) 6 4 6 4 s 3 2 is recovered.

Example 1X The interaction of one mole of 1.5-C1Si (C H (CH Si (C H C1 and two moles of potassium azide in the absence of a solvent at 100' C. for 24 hrs. yields Example X One mole of ClSn (CH C H.,O(CH C H Sn(CI-I C1 and two moles of lithium azide are refluxed in pyridine for 24 hrs. to yield The mono and difunction metalloid azides illustrated in Examples I-X have utility as insecticides, herbicides, fungicides, oil additives, blowing agents, and the like. They are also useful as chemical intermediates for the synthesis of metalloid phosphoranes, arsanes, and stibanes as described in copending application Serial No. 149,887, filed Nov. 3, 1961, now US. Patent 3,112,331, which is assigned to the same assignee as the present invention.

The azide compounds of this invention may be incorporated into resin compositions where they function as blowing agents during curing of the resins. The following example illustrates this use.

Example XI Twenty grams of an epoxy resin (having a melting point of 812 C., and epoxide equivalency of 190 to 210 and a viscosity of Z-S to Z-6 on the Gardner-Holdt scale) are admixed with about2.9 grams of tetraethylenepentamine as a catalyst therefor. Thereafter, 0.4 gram of trimethyl phosphite and 0.4 gram of triphenylsilyl azide are added to the mixture. The resultant mixture is heated to about C. whereupon the phosphite and azide react to lib erate nitrogen which passes out of the mixture and foams the resin. After about 10 minutes a firm, thermoset foamed resin results having a density of about O.20.3 grams per cc.

While the present invention has been described with respect to what at present are preferred embodiments thereof it will be understood, of course, that certain changes, substitutions, modifications and the like may be made therein without departing from the true scope of the invention as defined in the appended claims.

What is claimed is:

. Triphenylazidosilane.

. Dimethyldiazidosilane.

. Phenyltriazidogermane.

. Triethylazidostanne.

. Phenyldimethylazidostanne.

. l,4-bis(triazidosilyl)benzene.

. 1,3-bis(dimethylazidogermanyl)benzene.

. 4,4'-bis(phenyldiazidostannyl)diphenylether. 1,5-bis(diphenylazidosilyl)pentane.

10. p,p'-bis(dimethylazidostannyl)-2,2-diphenylpropane.

References Cited by the Examiner UNITED STATES PATENTS 2,712,026 6/ 1955 Schrader 260349 3,030,388 4/1962 Moore et al. 260-349 3,047,589 7/1962 Scott 260-349 OTHER REFERENCES Moeller, Inorganic Chemistry, pp. 661, 669, 670, 673 and 676 (Wiley) '(1952).

Rochow et al., J.A.C.S., Vol. 75, pp. 30993101 (1953).

WALTER A. MODANCE, Primary Examiner IRVING MARCUS, Examiner. 

1. TRIPHENYLAZIDOSILANE.
 6. 1,4-BIS(TRIAZIDOSILYL)BENZENE. 